Hydrogen activating apparatus

ABSTRACT

At least a pair of electrodes comprising semiconductors or a semiconductor compounds are arranged to be submerged in water or a liquid of a hydrogen-containing organic compound. Applying pulse electric power between the at least one pair of the electrodes activates hydrogen atoms contained in the water or the hydrogen-containing organic compound to produce hydrogen gas. The hydrogen activating apparatus thus constructed eliminates the necessity of doping electrolysis or the like for improving an electric conductivity of the water and allows production of hydrogen from materials containing hydrogen atoms such as water and the hydrogen-containing compound or the like with a low energy.

TECHNICAL FIELD

The present invention relates generally to a hydrogen activatingapparatus and particularly to a hydrogen activating apparatus having astructure for producing hydrogen by applying pulse electric powerbetween at least one pair of electrodes arranged to be immersed in wateror a hydrogen-containing organic compound liquid.

BACKGROUND ART

Recently, hydrogen has attracted attention as replicable fuel in placeof petroleum from point views of starvation of natural resources such aspetroleum and the greenhouse effect due to carbon dioxide.

Today, as such a method of producing hydrogen, 90% of industry-usehydrogen is produced from petroleum or natural gas by a steam reformingmethod or a partial oxidizing method.

As methods of producing hydrogen other than these methods, methods inwhich coal is used as crude material (COG method or the producergasifying method), a method of collecting by-product hydrogen from acommon salt electrolyzer, a method of electrolysis of water and the likehave conventionally been done.

Furthermore, recently, a thermochemical producing method or a method ofproducing hydrogen using sunlight have been studied.

As a method of producing hydrogen other than the methods describedabove, for example, there is a method of producing hydrogen by thermallydecomposing water. This method requires a reaction temperature of 1500°C. at the minimum and carrying out a reaction under a high temperatureof 4300° C. in order to increase a decomposition rate of water intohydrogen in which an energy consumption is large, which is not practicalexcept that a low cost power source is available.

On the other hand, there is also a possible method in whichalkaline-earth metals such as sodium, potassium, and manganese are dopedinto water and these metals are caused to chemically react with water.However, these metals are relatively expensive, and it is difficult toutilize these chemical reactions because these reactions are severe.

Furthermore, instead of water used in the method of electrolysis ofwater, electrolysis with hydrocarbon such as methanol can be considered.Hydrocarbon has a relatively low bonding energy between hydrogen andcarbon within a molecule, so that voltage differences necessary forthese electrolyses are low, but accompanied with generation ofby-products such as CO and CO₂ as reaction products, which requires acountermeasure for decomposing and removal of these products.

Furthermore, the inventors have promoted a study regarding an activestructure capable of producing hydrogen in which hydrogen is freed fromhydrogen bonds in water or hydrocarbon without externally applyingenergy.

As a hydrogen activating apparatus for producing hydrogen, an apparatusand a method disclosed in a U.S. Patent are known (for example, see U.S.Pat. No. 6,126,794 and U.S. Pat. No. 6,419,815). This apparatus isconstructed such that at least one pair of electrodes are immerged inwater in a container containing the water in such a condition that theelectrodes are made close to each other with respect to a distancetherebetween, wherein when pulse electric power is applied between theelectrodes, orthohydrogen (generating heat of combustion which is largerthan that of parahydrogen) is produced, and when pulse electric power issupplied to a coil arranged at an upper part of water in addition ofapplying the pulse electric power between the electrodes, theparahydrogen is produced.

In this hydrogen activating apparatus, an input power is 12V×300 mA (alow voltage×a high current), and bubbles of oxygen and hydrogen areproduced at the middle between the electrode plates though its principlehas not been disclosed. In other words, it is described that water canbe decomposed.

However, in the case of using the pulse of 12 V with 300 mA, when acurrent of 300 mA is conducted through the electrode plates, adecomposition action of water occurs due to the current which is similarto that occurs in the electrolysis. In other words, the powerconsumption becomes large.

Furthermore, when water is subject to electrolysis, to improve theelectric conductivity of the solution, generally, electrolyte such asalkali metal (NaOH, KOH, or the like) is doped to increase a currentdensity, so that a running cost regarding medicine is high.

Then, if water is subject to electrolysis without doping electrolyte,with utilizing super pure water as water, an amount of produced hydrogenbecomes low and the cost is high. On the other hand, if service water,which is cheap and harmless, is used, it is difficult to efficientlyutilize water because the current density at the electrodes cannot bemade high.

The present invention is provided to solve the above-described problemsand aims to provide a hydrogen activating apparatus which can producehydrogen from a substance containing hydrogen atoms such as water orhydrogen-containing organic compound with low energy and which requiresno dopant of electrolyte or the like into water to improve an electricconductivity.

DISCLOSURE OF THE INVENTION

A hydrogen activating apparatus as an aspect of the present invention ischaracterized by a structure in which at least one pair of electrodescomprising semiconductor or a semiconductor compound arranged andimmerged in water or a liquid of hydrogen-containing organic compoundare supplied with pulse electric power therebetween to activate hydrogenatoms contained in said water or the hydrogen-containing organiccompound to generate hydrogen gas.

According to the hydrogen activating apparatus having such a structure:

(1) When pulse electric power is applied between at least one pair ofelectrodes comprising semiconductor or a semiconductor compound andbeing arranged and immersed in water or a hydrogen-containing organiccompound, energy of electromagnetic waves derived from the pulseelectric power is absorbed in hydrogen atoms having magnetic poles,which readily activates the hydrogen atoms, so that hydrogen atoms areeasily freed from water or hydrogen-containing organic compound toproduce hydrogen (molecules).

(2) Further, applying the pulse electric power that does not directlyrelate to supplying electrons makes it possible to readily activate anddecompose hydrogen atoms even from general service water, distilledwater, or a hydrogen-containing organic compound without contaminationof the environment at a lower energy.

Accordingly, there is provided a hydrogen activating apparatus capableof producing hydrogen from substances containing hydrogen atom such aswater or hydrogen-containing organic compound or the like withoutnecessity of doping electrolyte for improving an electric conductivityat a low energy.

Here, the description “the pulse electric power that does not directlyrelate to supplying electrons” means pulse electric power of (a highvoltage)×(a low current) (not zero, but almost no current).Conventionally, methods for obtaining hydrogen by electrolysis of wateror hydrogen-containing organic compound requires an operation conditionof (a low voltage)×(a high current) because it is necessary to make acurrent density at the electrodes high. On the other hand, according tothe present invention, a semiconductor material which does not easilyallow a current to flow therein is used for the electrodes to which thepulse electric power of (a high voltage)×(a low current) is applied foreach pair of electrodes.

In the hydrogen activating apparatus mentioned above, it is desirablethat the semiconductor or the semiconductor compound forming theelectrodes contains at least one of kinds of silicon, germanium,gallium, phosphorescence, arsenide, cadmium, sulfur, and selenium.

The electrodes are constructed with the electrodes made of at least onekind of the elements, which provides the production of hydrogen with alower energy than that provided by the conventional electrolysis ofwater. Here, the element herein means an element which does not has apurity of 100%, but contains a small amount of impurity.

Furthermore, it is preferable that the above-described hydrogenactivating apparatus is characterized in that a configuration of theelectrodes is a plate or a sleeve.

Conventionally, in the electrolysis of water, it was necessary to makethe current density at electrodes larger, which required a complicatedshape at surface areas of electrodes such as porous plates and metalmesh, which results in a high manufacturing cost. On the other hand,according to the present invention, the electrodes are formed to have ashape of plate or a sleeve, which can simplify the shape of theelectrodes because of the low current density. This reduces themanufacturing cost.

Further, it is preferable that the above-described hydrogen activatingapparatus is characterized by the structure enabling that the hydrogenactivating apparatus is stopped after the pulse electric power isapplied between the electrodes for a predetermined interval, then, amaterial of the electrode of the positive electrode and a material ofthe electrode of the negative electrode are exchanged with each other,and after that, the pulse electric power is applied again.

The hydrogen activating apparatus constructed as mentioned above candecompose water in such a condition that there is no loss at theelectrodes outside the system. More specifically, when the pulseelectric power is applied to the electrodes to the electrodes for apredetermined interval, the material of the electrode on the side of thenegative electrode is dissolved into the liquid and deposited on theelectrode on the side of positive pole (the side of earth). Then, thematerial of the electrode on the positive polarity side (on the side ofearth) is made to be the material of the electrode on the negativepolarity side. Thus, the material of the electrode which was first onthe negative polarity side is made to be the material of the electrodeon the positive polarity side (earth), and then, the pulse electricpower is applied between the electrodes again, so that water can bedissolved in the condition that there is no loss outside the system.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a structural drawing illustrating the whole of a hydrogenactivating apparatus of an embodiment according to the presentinvention.

FIG. 2 illustrates a waveform characteristic of a pulse applied betweenelectrodes of the hydrogen activating apparatus of the embodimentaccording to the present invention.

FIG. 3 (a) is a drawing illustrating variation as time passes in anamount of the produced gas when the gas is produced from water with thehydrogen activating apparatus according to the present invention. FIG. 3(b) is a drawing graphing FIG. 3 (a). FIG. 3 (c) is a drawing in whichFIG. 3 (a) is modified to indicate a gas composition as time passes.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments according to the present invention will bedescribed with reference to FIGS. 1 to 3.

First, a hydrogen activating apparatus according to an embodimentaccording to the present invention will be described with reference toFIG. 1. Here, in this embodiment, a case that the hydrogen activatingapparatus is applied to the production of hydrogen from water will bedescribed.

A main part of the hydrogen activating apparatus according to thepresent invention is constructed, as shown in FIG. 1, with:

-   -   a container 1 filled with a predetermined amount of water;    -   electrodes 2 comprising four plates of silicon fixed in a        condition that they are immersed in the water;    -   a pulse oscillator 3 supplying pulse electric power to the        electrodes 2; and    -   a heater plate 4 for heating the water in the container 1.

The container 1 is constructed with an upper part 1 a of the containerhaving a conical shape and a bottom part 1 b of the container having asleeve shape.

Further, at the most upper part of the upper part 1 a of the containerhaving the conical shape, a tube 1 a 1 for introducing a gas producedwithin the container 1 into equipment collecting the gas by a method ofcollecting a gas over water at a rear stage (not shown).

Regarding the material of the container 1, glass is used in thisembodiment to provide a view of the inside. On the bottom part 1 b ofthe container, the upper part 1 a of the container is placed through anO ring (not shown), and integration is provided by pinching a flangepart of the upper part 1 a of the container and a flange part of thebottom part of the container with a clamp 1 c.

The electrodes 2 comprise four plates of electrodes 2 a to 2 d fixed ina condition that they are immersed in water, each being formed ofsilicon having a rectangular plate shape with the same dimension.

The electrodes 2 are used such that they are divided into two electrodes2 a and 2 c supplied with a negative voltage from a pulse oscillator 3mentioned later and two electrodes 2 b and 2 d connected to a positivepole (earth).

Further, since the positive pole is connected to the earth, a potentialof the positive electrode is always zero volts.

Furthermore, in this embodiment, two pairs of electrodes 2 a to 2 d areused. The number of electrodes can be adaptively changed to acquire anecessary amount of hydrogen. The number of electrodes can be changed ata unit of two. Further more, the shape of the electrodes is arectangular plate. However, sleeve electrodes are also usable.

Conventionally, in the electrolytic method of water, it was necessary tomake a current density at electrodes large, which requires forming thesurfaces of the electrodes to have a complicated form such as perforatedpanels and a metal mesh, resulting in a high manufacturing cost of theelectrodes. On the other hand, in the present invention, it is enoughthat the current density is small, which provides simplification of theshape of the electrodes, so that shaping the electrodes into platesreduces the manufacturing cost of the electrodes.

Furthermore, it is preferable that the surfaces of the electrodes areflat to allow the produced gas to be readily freed therefrom.Conventionally, electrodes with grooves, electrodes comprising metalmeshes, porous electrodes, electrodes with fins, rolling-shutterelectrodes, perforated panel electrodes, which were conventionally usedto increase current densities at surfaces of electrodes. However, thesurfaces of the electrodes are not flat, which impedes the produced gasupwardly from passing therethrough. This case requires a device forpromoting removal of babbles by a forced flow.

In this embodiment, silicon of a semiconductor is used as the materialof the electrodes. However, any semiconductor or semiconductor compoundcan be used which comprises at least one kind of element out of silicon,germanium, gallium, phosphorescence, cadmium, sulfur, and selenium.

Employing silicon of a semiconductor for the material forming theelectrodes provides the production of hydrogen with a lower energy thanthe conventional electrolysis of water with a smaller wear of theelectrodes than those made of a conductive material.

The pulse oscillator 3 is provided for supplying the pulse electricpower between two pairs of electrodes 2 a to 2 d. A pulse electric powergeneration circuit of the pulse oscillator 3 will be briefly describedhereinafter.

The pulse generation circuit of the pulse oscillator 3 that is one ofstructural elements of the present invention is usually used and known,and, for example, comprises a frequency converting circuit forconverting a frequency 50 Hz of a commercial frequency power supply upto 400 Hz, a step-up circuit comprising a transformer supplied with thepower having a converted frequency of 400 Hz to provide a high voltageat its output, and a pulse waveform shaping circuit for wave-shaping thestepped-up electric power to a triangular waveform.

The pulse electric power generation circuit of the pulse oscillator 3constructed as mentioned above first increases the frequency of an ACpower supply of 100 V from 50 Hz up to 400 Hz. The reason why thefrequency is stepped-up is to miniaturize the transformer in the step-upcircuit at the rear stage.

Next, the power having the converted frequency of 400 Hz is applied to aprimary of the transformer in the step-up circuit to output a highvoltage (for example, 1500 V) at the secondary side.

Further, the stepped-up electric power is applied to the pulse waveformshaping circuit to apply an output signal having the triangular waveformbetween the electrodes made of silicon arranged and immersed in thewater in the container 1.

Regarding a waveform characteristic of pulses of the pulse electricpower applied to the electrodes made of silicon will be described withreference FIG. 2.

The waveform characteristic of pulses is as shown in FIG. 2, such thatthe voltage applied between the electrodes made of silicon is a negativevoltage of 1500 V, and the current value is from 1 mA to 5 mA. This isthe pulse electric power of (a high voltage)×(a low current).

Further, a waveform of the pulse is a triangle in which an interval ofpeaks of triangles is 1/400 sec.

The heater plate 4 is an electric heater for heating the water in thecontainer 1 to heat the water in the container up to 95° C. by placingthe container 1 containing a predetermined amount of water on the platefrom the under side thereof. Heating further activates hydrogen atoms inwater by a mutual effect with the pulse electric power applied betweenthe electrodes.

Next, a principle of actuating hydrogen atoms when the pulse electricpower is applied to the water between the electrodes was supposed by theinventors and the like.

Hereinafter, this principle will be described.

Around a nucleus of a hydrogen atom (positive electric charge), oneelectron (a negative charge) revolves with rotation. Thus, Coulombforce, centrifugal force, and the like acts between the nucleus and theelectron in which an atomic space in which these pieces of forcepreserve balance among them.

When the pulse electric power is applied to water between the electrodesmade of silicon which is a semiconductor, energy of electromagneticwaves derived from the pulse electric power is absorbed by hydrogenatoms having magnetic poles, so that the hydrogen atoms become in anexcited condition.

Thus, the hydrogen atoms and oxygen atoms in water are bonded byhydrogen bond. The inventors considered that the bond between atoms,namely, the hydrogen atom and the oxygen atom, was disconnected due toweakened bond between hydrogen atoms and oxygen atoms, so that hydrogenatoms were freed from the oxygen, which causes bond of hydrogen atomswith each other resulting in hydrogen (molecule).

Next, with reference to FIGS. 1 and 3, an embodiment of decomposition ofwater with the hydrogen activating apparatus of an embodiment accordingto the present invention will be described in detail.

1. Structure of Hydrogen Activating Apparatus

(a) A container which is transparent and made of glass capable ofcontaining water of 400 mL.

(b) The electrodes which are rectangular and made of silicon, eachhaving dimensions of 20 W×50 L×0.5 t×4 (plates)

(c) The heater plate having a capacity for heating the water in thecontainer from 95° C. to 98° C.

(d) The pulse oscillator with −4.5 V×1.1 mA.

Further, copper wires used as wiring material for connecting theelectrodes 2 a to 2 d made of silicon to the pulse oscillator 3 areconnected by coating with adhesive to prevent reaction between thecopper wires and the silicon. The gas produced in the container 1 iscollected by a method of collecting a gas over water. The collected gasis analyzed by gas chromatography.

Next, a method of operation when hydrogen is actually produced with thishydrogen activating apparatus will be described.

(1) Fix four electrodes 2 a to 2 d made of silicon in the container 1 asshown in FIG. 1.

(2) When the pulse oscillator 3 is connected to four electrodes 2 a to 2d made of silicon, the electrodes 2 a and 2 c are connected to anegative electrode of the pulse oscillator 3, and the electrodes 2 b and2 d are connected to the positive electrode (earth) of the pulseoscillator 3.

(3) Next, water is poured in the container 1 until upper ends of fourelectrodes 2 a to 2 d made of silicon are submerged under the surface ofwater.

(4) The water in the container 1 is heated by placing the container onthe heater plate 4 up to 95° C.

(5) Not shown equipment for collecting a gas over water is provided atthe rear stage to collect the produced gas of which an amount of the gasis examined.

(6) A power switch of the pulse oscillator 3 is turned on. The pulseelectric power is applied to the electrodes 2 a to 2 d made of siliconfrom the pulse oscillator 3 for six hours. When the application of thepulse electric power for six hours has been done, the power switch ofthe pulse oscillator 3 is turned off.

FIG. 3 (a) illustrates variation, as time passes, in an amount of theproduced gas when the hydrogen activating apparatus is operated asmentioned above. FIG. 3 (b) shows a graphical indication of FIG. 3 (a),and FIG. 3 (c) shows the variation as time passes in FIG. 3 (a) isconverted into variation in a gas composition as time passes.

As understood from FIG. 3 (a) and FIG. 3 (b), application of the pulseelectric power to the electrodes made of silicon for six hours from thestart of application activates hydrogen atoms in water, so that hydrogenis separated from the oxygen atom as time passes.

Further, amounts of produced nitrogen and oxygen increased as timepassed, but were extremely lower than that of hydrogen. In other words,it was understood that hydrogen atoms were selectively activated.

Furthermore, it was seen that hydrogen was produced at the negativeelectrode side and that silicon was deposited at the side of thepositive electrode (earth side). However, when, for example, a consumedamount of silicon of the electrode is large (for example, 10%), theexchanging the materials of electrodes of the positive and negativeelectrodes with each other enabled the decomposition of the waterwithout loss of silicon in the system outside the system.

Further, in the case that water was decomposed without exchanging thematerials of electrodes between the positive and negative electrodes,the production of hydrogen was unable to be observed after about 30hours. On the other hand, when the water was decomposed with exchange ofthe materials of electrodes between the positive and negativeelectrodes, the production of hydrogen was able to be observed afterabout 100 hours.

The presence and the absence of the deposition of silicon at thepositive electrode (earth) was confirmed by observing sample chips ofthe positive electrodes (earth) after a predetermined time intervalelapsed after the start of application of the pulse electric power witha scanning electron microscope (SEM) with X ray micro-analyzer.

According to the hydrogen activating apparatus of an embodiment havingsuch a structure and effect, the use of silicon which is a semiconductorfor the electrodes and the application of the pulse electric powerobtained by (a high voltage)×(a low current), which is different fromthe conventional art, provides the followings:

(1) By not electrolysis of water, hydrogen was able to be preferablyproduced with low energy by selectively activating only hydrogen atoms.

(2) The application of the pulse electric power provided by (a highvoltage)×(a low current) produces deposition of silicon at the positiveelectrode (earth side). However, after a predetermined time interval hadelapsed, loss of silicon outside the system was prevented by making thematerial of positive electrode be the material of negative electrode andmaking the material of the negative electrode be a positive electrodewas able to prevent loss of silicon outside the system.

As mentioned above, the hydrogen activating apparatus of an embodimenthas been described. The hydrogen activating apparatus according to thepresent invention is not limited to this, but can be provided withoccasional modification without departing from the technical scope ofthe present invention.

For example, the pulse electric power generated by the pulse oscillatormay have any waveform other than the triangle form as long as the pulseelectric power is provided with (a negative high voltage×a low current).

A method of preventing the loss of silicon outside the system may beprovided by exchanging the polarities of electrodes with an electroniccircuit without exchanging the materials of the positive electrodes(earth) and the negative electrodes.

According to the present invention with the structure and operation asabove described, there is provided a hydrogen activating apparatuscapable of producing hydrogen from materials containing hydrogen atomssuch as water, hydrogen-containing organic compounds, or the like with alow energy without necessity of doping electrolyte or the like forimproving the electrical conductivity.

INDUSTRIAL APPLICABILITY

Hydrogen, which can be produced by the method with high energyefficiency with a simple equipment structure using the hydrogenactivating apparatus according to the present invention, is expected tobe used in all industrial fields as a fuel, replaceable for fossil fuel,used in fuel cells or the like.

1. A hydrogen activating apparatus characterized by a structure thatpulse electric power is applied between at least a pair of electrodescomprising a semiconductor or a semiconductor compound and beingarranged to be submerged in water or a liquid of hydrogen-containingorganic compound to activate hydrogen atoms contained in the water orthe hydrogen-containing organic compound to produce hydrogen gas.
 2. Thehydrogen activating apparatus as claimed in claim 1, wherein thesemiconductor or the semiconductor compound forming the electrodes,comprises at least one kind of element out of silicon, germanium,gallium, phosphorus, arsenic, cadmium, sulfur, and selenium.
 3. Thehydrogen activating apparatus as claimed in claim 1, wherein shapes ofthe electrodes are plates or sleeves.
 4. The hydrogen activatingapparatus as claimed in claim 1, characterized by the structure enablingthat the hydrogen activating apparatus is stopped after applying thepulse electric power between the electrodes for a predetermined timeinterval, an electrode material of the positive electrode and anelectrode material of the negative electrodes, which construct theelectrodes, are exchanged with each other, and then, the pulse electricpower is applied again.